Preparation of monomeric glycidyl polyethers of polyhydric phenols



United States Patent O 's ce 33222:

ported that monomeric glycidyl polyethers have been obtained in yields as high as 81 mole percent or 70% v 2 096 as expressed in parts by weight of the reaction product. Another method which has been proposed in order to PREPARATION OF MONOMERIC GLYCIDYL 5 increase the yields of the monomeric glycidyl polyethers POLYETHERS 0F POLYHYDRIC PHENOLS is one wherein only stoichiometric amounts of aqueous alkali have been used to neutralize the hydrogen chlogggfi gfa ggafl g gk giz fi gzg gfi ride formed in the etherification reaction. Adding only a a stoichiometric amount of aqueous alkali, however,

N0 Drawillg- Filed y 1957, i- 658,232 10 results in an incomplete dehydrochlorination of the inter- I mediate chlorohydrin ether. The dehydrohalogenation 16 Clams 260 348'6) reaction is an equilibrium reaction and may be illustrated by the following equation wherein the intermediate chlorohydrin ether has been formed by reacting epichloro- This invention relates to the production of glycidyl hydrin with Bisphenol A. polyethers of polyhydric phenols by reacting a polyhydric phenol with epichlorohydrin m form a glycidyl polyether CHrCECHrOOOCHrCECHHNaOH? 7 comprising as the principal product monomeric glycidyl polyether and only minor amounts of polymeric glycidyl 01 OH H 01 ethers containing two or more aromatic. hydrocarbon 2o radicals alternating with glyceryl groups which are con- 0Hr-OH-0Hi0--0 0Hi-CH-OHi+2Na l+ nected therewith through ether oxygen atoms.

More particularly, the invention is concerned with obtaining a reaction product containing as much as 85% In order to drive the reaction to completion to the by weight of monomeric glycidyl polyether and in miniright, it is necessary to add an excess of the stcichiometric mizing the formation of polymeric glycidyl polyethers. amount of caustic required for dehydrochlorination. On Glycidyl ethers of polyhydric phenols have usually the other hand, an excess amount of alkali is to be been prepared by reacting a monoxyglycerol halohydrin avoided since it tends to increase the side reactions which with a phenol in the presence of an alkali catalyst. For decreas'e'the yield of the monomeric glycidyl polyethers example, epichlorohydrin reacts with bis(4-hydroxy and are detrimental to the quality of said polyethers phenyl)dimethylmethane, commonly known as Bisphenol obtained.-

A, in the presence of an alkali to form in addition to Another proposal has been to add the aqueous alkali polymeric reaction products, the monomeric glycidyl ether in amounts small enough to maintain the reaction mixof bis(4-hydroxy phenyl)dimethylmethane. This reacture at an alkalinity less than that which colors phenoltion may be represented by the following equation: phthalein.

CHI

As represented by this equation one mole of epichloro- 46 Still another proposal has been to carry out the reachydrin is required for reaction with each phenolic hytion in the presence of hydroxylated solvents such as droxy group. It has been found, however, that if these ethanol. ratios are employed the yield of monomeric glycidyl While these processes have alleged an increase in the polyether would be exceedingly small, at most about yield of monomeric glycidyl polyethers, in actuality the 10% by weight of the reaction product. The product 50 yields have not exceeded about 70% by weight of the rewould comprise predominately of high molecular weight action product. These proposed processes are also defipolymers and condensation reaction products containing L cient in that recovery of only a portion of the excess two or more aromatic hydrocarbon radicals alternating epihalohydrin is possible, at most about 85%. with glyceryl groups which are connected therewith I have now found a new and novel method of preparthrough ether oxygen atoms. The following is a repreing monomeric glycidyl polyethers which eliminates the sentative structural formula of the high molecular weight difficulties present in the processes formerly proposed. polymers obtained when two moles of epichlorohydrin By my new and novel method there are obtained yields per mole ofBisphenolAarereacted. Y as high as '85 percent by weight of the monomeric CH5 J I a. An

cm-on-omwO-d-G- where n has avalue of from 1 to 15. glycidyl polyether based on the weight of the reaction In order to increase the yields of monomeric glycidyl product.

polyethers, it has been proposed to use an excess of epi- The proposed process also affords a method wherein chlorohydrin, corresponding to from 2 to 3 times the the different reaction steps are integrated into a practistoichiometric amount. By this means it has been re-' cally continuous process in which there is efiected recov:

cry of substantially 100% of the excess epichlorohydrin. The process is also advantageous in that recovery of CI-CHv-CH-CHrO CH! r r I practically 100% of the excess epihalohydrin eliminates k a source of side reactions which are detrimental to the C yield and quality of the monomeric glycidyl polyethers. 5

0-011 CH-CH 01 OH OH 01 CHr-(EH GHQ-0 CH -(g H CH:

o-w 'M*: 1

C. (ilHs (BB1 H 0 o-oH 'on-oH 01+M+0- 0M+ O1 CHPEH .0 r on g it on;

H (j} H (1:

Hr (3H5 v Chlorohydrin ether Another advantage is that the process affords a method According to these equations the phenoxide intermediby which lower viscosity products can be obtained in ate is continuously regenerated until all the phenolic comparison with prior proposed methods. hydroxyl groups have reacted with the epichlorohydrin.

My invention is based on the discovery that the yield Second stage:

Cl-GHr-CH-CHa-O CH -ooH,on-onro1+2 vsort Am A $11 of monomeric glycidyl polyether is unexpectedly in- It has now been found that formation of undesirable creased by carrying out the reaction between epichloropolymerization and condensation reaction products may hydrin and the polyhydric phenol in two stages, in the be substantially eliminated by conducting the stage one first stage forming the intermediate chlorohydrin ether reaction in an anhydrous medium in the presence of a by reacting the phenol and the epichlorohydrin under quaternary ammonium catalyst whereby substantially all substantially anhydrous conditions and in the presence of of the phenolic hydroxyl groups react with the epichloa catalytic amount of a quatern ry mm ni m c mrohydrin to form the corresponding halohydrin ether P and in the Second Stage ming the monomeric and by removing the unreacted epihalohydrin prior to y y Polyether by dehydrohalhgehatihg the ihtel'methe stage two dehydrohalogenation. It is essential to diate halohydrin. this invention that the stage one reaction be carried on It is believed that the following reactions occur durin a substantially anhydrous medium. It has also been iflg the first Stage as typically illustrated y the fOlIOW- found advantageous to carry out the reaction in a meing equations, wherein MX is a quat rn ry ammonium dium free of hydroxylated solvents in order to insure compound. that the epihalohydrin will not undergo a series of side First stage: reactions with subsequent formation of products which (a) MX are not capable of easy removal from the system. These 0 X 1 products contaminate the system, lowering the yield and i quality of the final product. Eplchbmhydrm The following equation represents the reaction which (b) epihalohydrin undergoes in the presence of a hydroxyl- 2GHr-CH-CH:+OH on V ated solvent such as ethanol.

x -M+ 01 r v0 BisphenolA ClCHr-'(lJH-CHr-OC|Hs Qi H/CHCHT'OOZHA OH 0 (Intermediate ehlorohydrin ether) (Ethyl glycidyl ether) ant The ethyl glycidyl ether boils at 126 0., which is near the boiling point of epichlorohydrin (117 C.). In A distilling off the excess epichlorohydrin any ethyl glycidyl (6) ether or its intermediate chlorohydrin other which has formed is recycled along with the epichlorohydrin back Mho CH; O X P2057011 into the system. The glycidyl ether undergoes a reac- O tion with the phenol to give an undesirable non-epoxy terminated product as typically illustrated by the following equation.

cina-o-om-ore-om-o-gc -ooH,on-oH,-oo,m

in p a. is

seas-nae The non-epoxy terminated product increases the epoxy benzyl trimethyl ammonium chloride, tetraethanol equivalent weight of the final product and also impairs monium chloride, tetraethanol ammonium hydroxide, and

the functionality of the product. This is manifested by dodecyl dimethylbenzyl ammonium naphthenateeffect a;

a lower heat distortion temperature and fiexural lower quantitative coupling of the epihalohydn'n and a P y strength when the product is reacted with standard hardhydfie Phenol in a Substantially anhydrous medium f ening agents. of organic hydroxylated solvents forming the intermediate Water in excess of 1% b i ht in h fi stage f chlorohydrin ether to the exclusion of substantialfor'rnathe reaction system separates out as a water phase near tion of undesirable polymerie Side Produetsl Further the end of the coupling reaction. The water in sepmore, the quaternary ammonium c mpounds do not in arating as a distinct phase extracts substantial amounts 19 corporate into the glycidyl polyether Pmduct and hence of the coupling catalyst from the organic reaction meare easily removed from h system g dium, thus hindering the reaction between the epichloro- The quaternary ammomum P f this y a 9 hydrin and the polyhydric phenol, are also advantageous as catalysts as they do not pre- The present process insures a quantitative coupling clpitate i of the Teactlon med1um These catalysts] of the epihalohy'drin and the phenolic compound. Moremam.avaflab1? t e for efiectwgy g the over, by effecting. a quantitative coupling in stage one couphng reaction essennauy topomplehont i othgl. to form the chlorohydrinether to the substantial exhang base catalysts formerly proposed are m b fii clusion of condensation and polymerization products, usema'substantlany anhydrmis y q i med1um the unreacted epihalohydrin may be easily removed beas h undergo a reigtlon with Th mterinedlate h -i" fore proceeding to the dehydrohalogenation stage. 20 hy-dnn ether iormed m the-coupling Ramon bi-ati-veen the It is essential to recover substantially all of the uneplchlomhydnn and the Sald phenol and preclpltate out reacted epihalohydzin, for if present in the dehydrohalogenation step, it will react with the alkali solution to form such heat sensitivecompounds as glycido'l', as' shown in tion may be typically illustrated by the following equation wherein R is a fragment of a polyhydric phenol.

of the reaction medium as insoluble chlorides. This reactthe following equation. R-OCHrCHCHi+NaOH- H20 H l V I CH2CH-CH2C1+MOH -v R O CHB CH GHQ+NBCI FHTO orrr-on ornon+on--on cn= t a H OH 5 As illustrated by the foregoing equation, therefore, the 'Gmidol Glycerol base catalysts formerly used, as exemplified by sodium hy-. droxide on reaction with the intermediate ether form chlo- T glycldol formed accordmg thls eqilauon 1S rides which precipitates out of the reaction medium. The five to It tend? polymenge forming undeslral.) 6 reaction of the base to form insoluble chlorides removes prodlicts whlcil i m m the glycldyl polyetherstflius the base as an effective coupling catalyst. This eliminacreasmg the vlswslty of these ethers' Moreover It Is tion results on incomplete coupling of the epichlorohydrin essary to recover the unreacted epihalohydrin in order to make the process commercially feasible. and the polyhydnc phenol' It is also essential to this process that a quaternary amthe reaction medium in the first stage should be sufiicient momum i be employed to eifect the couphng 4 at least, to color phenolph-thalein. Preferably, the quaterof the eplhalohydnn and the polyhydnc phenol It has nary ammonium compounds are employed in concentrabeen found that catalysts usually employed in this type 1 a reaction are unsuitable as they undergo side reactions with 3323 25 2313? and mole per each phenolic The concentration of the ammonium compounds in the epihalohydrin to form undesirable highr molecular It has also been found that the first stage coupling re-.

weight derivatives. One such side reaction is represented action should be conducted at temperatures not exceedby the following equations: ing 60 C. Temperatures in excess of 60 C. lead to the formation of undesirable polymeric compounds. Tem

NaOH 0 0 -CH H HooH -CH-OE N C] I a 1 s 2+ 8 peratures of about 40 C. or lower have been found most.

0 0 suitable since at lower temperatures better yields and;

' CmOH better quality glycidyl polyethers are obtained. The lower NaOH t 1 the temperature, however, the longer is the reaction time E7 cmnecessary for the first stage coupling to occur. For ex- 0 ample, at room temperature, about 25 C., the time of where n has a value of from 1- to 20. reaction is 72 hours.

The base catalysts formerly proposed are also undesir- Following the removal of excess epihalohydrin from the able for they cause premature formationofglycidy'lpolyireachgm e u p standard low pressure, ort c nothers which, being in admixture with the unreacted phenol tact time d1st1llat1on technlques, the dehydrochlorinatlon and chlorohydrin ethers, react therewith to form und i of the intermediate halohydrin ether can be continuously able high molecular weight reaction products. These recarried Out in liquid medium using s ch as a 20% actions are illustrated by the following equationsz excess of a stoichiometnc amount of a base. It is preferred, however, that a 5% excess of the stoichiometric O H CH--CH C1 MOH-;T Clog CH OR C T- 2 amount be used. The liquid med1um is preferably am x- H H g ture of solvents comprising (1) a volatile, water-soluble ClCHp-GH -CHrO R0-OH=-OH Ht=talcohol or ketone, which is a solvent for the epihalohydrin 0 and the aqueous caustic, such as ethanol, acetoneisooions-Cn-oma)n-o oni-o;gr on,+non-o carom-011w E. 0 H l 2MOH C-ICH'g-CH- OHPOROOHz -OH-CHr-OR-O-OHz-CH-CH;

H Hf H 1 CHr-OH-CHr-O R-O CHr-CHOHg-O R-0-oHT-oH-=- 3H+2Mo1+2rr,o

I have now fou'ndthat the quatemary' ammonium type" propanol, dioxane, but'anol, and methanol, and (2 a by compounds such as tetramethyl ammonium chloride, V drocarbon o'r ether which is relatively'insoluble in waterf 7 but which is a solvent for the glycidyl ether, such as toluene, xylene and isopropyl ether.

By the use of a mixture of water-soluble and waterinsoluble solvents, the base is precluded from attacking and destroying the glycidyl polyethers. If only a watersoluble solvent such as methanol were used there would he a completely homogeneous solution in which the base would readily attack the glycidyl polyether to produce hydrolyzed or partially polymerized by-products. On the other hand, if only a water-insoluble solvent were used, the rate of dehydrochlorination would be too slow to be practical.

The ratio of water-insoluble solvent to water-soluble solvent may be varied between about a 1:1 and 3:1 ratio by weight.

The usual method of dehydrochlorination of chlorohydrin ether has been carried out batchwise. It has now been found that the dehydrochlorination may be carried out by a continuous process which allows for the recycling of the solvents used to solvate the intermediate chlorohydrin ether. This continuous process affords a method by which the dehydrohalogenation may be carried out more quickly and economically than the batch processes used heretofore. The advantages inherent in this continuous aspect of the process make it more feasible for the commercial preparation of a reaction product containing a major amount of monomeric glycidyl polyether.

It has also been found that the dehydrochlorination may be advantageously carried out using up to about 20% in excess of the stoichiometric amount of base with the concentration of the caustic solution being about 18% or less. The concentration of the caustic solution is kept at 18% or lower, 'for if a solution of higher concentration were used, sodium chloride formed in the dehydrohalogenating step would precipitate out of solution. The salt precipitate would tend to clog the apparatus necessitating a series of steps to eliminate the precipitate from the system. A solution of 18% concentration or less also provides a sufiicient amount of water to wash out substantially all of the quaternary ammonium catalyst from the glycidyl polyether product. It is also advantageous to add the caustic solution in two stages. Usually, 75% of the total amount of caustic is added in the first stage and 25% of the caustic is added in the second stage. Each addition of caustic is followed by a settling and decantation step to eliminate the brine layer.

The two-stage addition of caustic is used in the dehydrochlorination step in order to (1) prevent damage to the intermediate other product which would occur as a result of a single addition of a caustic solution and (2) to enable removal of the brine solution after each addition to insure that the dehydrochlorination reaction goes to completion.

The speed of the dehydrohalogenation reaction depends to a large extent on the temperature. Temperatures of between 4070 C. are preferred. At these temperatures the density of the water phase and organic phase is such that there is a clear separation of the phases into two layers, with the aqueous brine being the bottom layer.

The dehydrochlorination compounds which may be used in the dehydrohalogenation step are the caustics such as sodium and potassium hydroxide.

By the term polyhydric phenols there is intended to be included the mononuclear polyhydric phenols such as resorcinol and pyrogallol, the dior polynuclear phenols such as the bisphenols described in the Bender et a]. United States Patent No. 2,506,486 and polyphenylols such as the novolak condensation product of a phenol and a saturated or unsaturated aldehyde containing an average of from 3 to 20 or more phenylol groups per molecule (cf. book by T. S. Carswell entitled Pheno plasts, published in 1947 by Interscience Publishers of NewYork). Exemplary of suitable polyphenylols derived from a phenol and an unsaturated aldehyde such as acrolein, are the triphenylols, pentaphenylols and heptaphenylols described in copending application S.N. 368,514, filed July 16, 1953, noW U.S. Patent 2,885,385 and copending application S.N. 422,275, filed April 9, 1954, now U.S. Patent 2,801,989, by A. G. Farnham.

The phenols may contain alkyl or aryl ring substituents or halogens, as exemplified by the alltyl resorcinols, the tribromo resorcinol and the diphenols containing alkyl and halogen substituents on the aromatic ring (Bender et al., U.S. Patent 2,506,486).

The polyhydric polynuclear phenols can consist of 2 or more phenols connected by such groups as methylene, alkyl, alkylene or sulfone. The connecting groups are further exemplified by the compounds having the following formulas.

Bis (4-hydroxy phenyl methane Bis t-hydroxy phenyl) dtmethylmethane Dthydroxy diphenyl snrone A trisphenol having the formula A tetraphenol having the formula OH OH The epihalohydrin of the present invention is preferably epichlorohydrin. An excess of the stoichiometric amount of epichlorohydrin is used in the reaction, preferably at least 3 moles per each phenolic hydroxyl group. The amount of epihalohydrin is dependent in part on the catalyst and the reaction temperature. For example, with tetramethyl ammonium chloride as the catalyst, 6 moles of epichlorohydrin were used per mole of Bisphenol A with a reaction temperature of 40 C. and time of reaction, 26 hours.

The first stage of this process is conducted by admixing a polyhydric phenol with excess epichlorohydrin in the presence of a quaternary ammonium catalyst. The mixture is heated to a temperature of about 40 C. The

time required to complete the first stage reaction using 0.07 mole of catalyst per mole of Bisphenol A is about 26 hours. The progress of the first stage coupling reaction may be determined by an epoxy analysis of the unreacted epihalohydrin and by an ultra-violet spectrophotometric analysis by which the percent of unreacted phenolic hydroxyl groups is measured. After completion of the coupling reaction which is indicated by the substantial absence of phenolic hydroxyl groups, the unreacted epiehlorohydrin is distilled off under a vacuum estates.

chlorohydrindistillate 'is treated to convert any glycerol dichlorohydrin'which may have formed in the reaction to epichlorohydr'in and. thereafter the distillate is recycled to the stage one reaction medium. Fromthis point on the process becomes continuous. The residue, a viscous liquid containing the chlorohydriniether. of the pclyhydric phenol is dissolved in a mixture of solvents, for example toluene and ethanol. The solventsare used in mixtures ranging between 1:1 and 3:1 parts by weight of waterinsoluble solvents to wateosoluble solvents and in amounts such that a 45%" solution with respect to the, chlorohydrin ether is formed. I

Instead of toluene, xylene or isopropyl ether may be used, and instead of ethanol, acetone, dioxane, isopropanol, b-utanol, or methanol may be used.

To the solvated'residue there is added in two stages a water solution containing 18% or less-by weight of a caustic at temperatures ranging from" 40 70" C., preferably 55 60 C. In stageone, 75 of the solution is added. In stage two the remaining amount of solution is added. The amount of caustic solution: ranges from a stoichiometric amount to 20% in excess of the stoi-f chiometric amount necessary to' dehydrochlorin'ate the intermediate chlorohydrin others.

The organiclayer containing the organic solvents and a the crude glycidyl polyether product is'decanted from the brine layer after each addition of caustic solution. The organic solvent is stripped from the crude glycidyl polyether product under reduced pressures and at a residue temperature of about 120 C. The organic" solvent which is separated from the product is recycled. The residue containing the glycidyl polyether is finally stripped under a vacuum at a temperature of about 150 C. to obtain the final glycidyl polyether product. The product is analyzed for its epoxy equivalent by heating one gram of the ether product at the boiling point of pyridine for 20 minutes in the presence of an excess of pyridine containing pyridine hydrochloride (made by adding 16 cc. of concentrated hydrochloric acid per liter of pyridine). The excess pyridine hydrochloride is-back titrated with 01 Normal sodium hydroxide using phenol phthalein as the indicator. One mole of the hydrochloric acidis considered equivalent to one epoxide group. The result is expressed as epoxy equivalent which means'the number of grams of product that contain one mole equivalent epoxy. The yield of the monomeric glycidylpolyether may be expressed as percent by weight-based on the weight of the total product obtained. The percent by weight is calculated on the basis of the epoxyequivalent.

The following examples further illustrate. the process of this invention withoutlimitingin any way the scope of-.-the invention.

Example].

One mole of bis(4-1ydro xy phenyDdirnethylmethane, 6 moles of epichlorohydrin and 0. 07 mole of tetramethyl ammonium chloride were admixed and heated. The temperature was maintained at 40 C; for 26 hours. This step is a mildly exothermic reaction releasing approximately 76 B.t.u. per pound of charge; The progress of the reaction was followed'by measuring the content of unreacted bisphenol in the reaction medium. The

ator at, a pressure maintained between;2 5-j30 mm. The

solution was fed into two overflow reactors at an average temperature of the material was -maintained. at 130 C. Unreacted epichlorohydrin was evaporated at the rate of 125.5 lbs. per hour and subsequently treated with sodium hydroxide or lime to. convert any glycerol dichlorohydrin which may have formed in the reaction to epichlorohydrin. Epichlorohydrin thusly treated, was recycled for reaction with additional phenolic material. The intermediate chlorohydrin ether. a viscous liquid, was fed to the solvation line mixer tank at'a rate of" 121 lbs. per hour and solyated with a recycle toluene-ethanol mixture. The toluene-ethanol recycle was fed into the solvation line mixer at the rate of 128'lbs. per hour after which the solvated mixture was transferred to a cooler where the- Atthis stage the toluene-ethanol ratio was adjusted to 3 :1 and furtheradditions of solvent were made to obtain a solution containing a solids content of 45 percent. The

' rate'of'feed of the alcohol into the adjusting tank was 6.4 lbs. per hour. The rate'of feed of the: toluene was 4.1 lbs. per hour, while the rate of feed of the solution from the cooler into the reactor feed mix adjusting tank was 121 lbs. per hour. From the adjusting tank the rate of 257.4 lbs. per hour. In these reactors the solution was treated with a-caustic solution having a concentration of: 18% by-weight of sodium hydroxide. Sufiicient caustic was. added to provide'an excess of 5% of thestoichiometric amount required for complete dehydrochlorination of. the intermediate ethers.

Seventy-five percent: of thel total caustic was added to the first reactor at a rate of 82.5 lbs. per hour. The remainingcaustiowas: addedv to the second reactor also at 27.5 lbs. per hour. 'Aft'erieach addition of caustic the material was fed first into a holding tank and then into a decantation tankwhere the brine'layerwasseparated from the organic layer. The dehydrochlorinating steps were carried out at atemperature of 55 C. The rate of'feedfrom the firstreactor into the secondreactor was maintained at an average of 257.4 lbs. per hour. Additional-alcohol was also addedto second reactor at the rateot 16 lbs. per hour in order to maintain a cienttoprovide amaterialitemperature of C. The

solventspwerestr-ipped from the glycidyl polyether product-.inthisstep and recycled back to the solvation stage. The crude. glycidyl polyetherwas finally stripped under a pressure of about 30 mm. at C. to the final product.

Thestripped glycidyl polyether of Bisphenol A had an epoxyequivalencyof:1'89, a viscosity of 12,100 centisto kes and a color'on the Gardner scale of 5. Based on the epoxy equivalency the content of monomeric glycidyl polyether was'calculatedas 78% by weight of the total weight of the product. The remaining product comprised essentially high molecular weight polymers. 'Iheamountofcatalyst taken up by the product as manitested by-the amount'of-nitrogen-present in the product was less than 0.01%. The amount 'of unreactedepi chlorohydrin recovered was 100%. V j

The glycidyl' polyether product was f hardened with 4,4-methylene dianiline by admixing the two components andcur ing for 20 hours at 85 C and thereafter anneal 5 ing-for 3-. hours at C; Sufiicient quantity ot reactants was used to; provide one equivalent'of epoxy .per

eachgaminohydrogen: The glycidyl polyether product ural "strength at roomtemperaturewas 1 16,900 psi. 1329. C. the .flexural strength was 8030=p .s.i.

1 1 Example ll One mole of bis(4-hydroxy phenyDdimethylmethane and 6 moles of epichlorohydrin were admixed in the presence of 0.07 mole of benzyl trimethyl ammonium chloride. The mixture was heated at 40 C. for 20 hours whereby the phenol and epichlorohydrin reacted to form the corresponding chlorohydrin ether product. Thirty thousand pounds of the precoupled chlorohydrin ether prepared as noted above were continuously dehydrochlorinated to form the glycidyl polyether of bis(4- hydroxy phenyl)dimethylrnethane by a process as defined in Example I.

The glycidyl polyether product had an epoxy equivalency of 183, a viscosity of 10,000 centistokes and a color on the Gardner scale of 5. Based on the epoxy equivalency the content of monomeric glycidyl polyether was calculated as 84.5% by weight of thetotal weight of the product. The remaining product comprised essentially high molecular weight polymers. The product was free of any nitrogen indicating that no amount of catalyst remained in the product. There was a 100% recovery of the unreacted epichlorohydrin.

The glycidyl polyether product was hardened with 4,4'-methylene dianiline by admixing the two components and curing for 20 hours at 85 C. and thereafter annealing for 3 hours at 160 C. Sufiicient quantity of reactants was used to provide one equivalent of epoxy per each amino hydrogen. Using standard ASTM procedures, the glycidyl polycther was found to have a heat distortion in degrees centigrade of 163. The flexural strength at room temperature was 17,200 p.s.i. At 132 C., the flexural strength was 8400 p.s.i.

What is claimed is:

1. Process for the preparation of glycidyl polyethers of polyhydric phenols which comprises reacting a substantially anhydrous mixture containing a polyhydric phenol, epichlorohydrin in an amount sufficient to provide at least about 3 moles of epichlorohydrin per phenolic hydroxyl group, and a catalytic amount of a base-generating quaternary ammonium compound on reaction with epichlorohydrin, until substantially all of the said phenol has been converted to its chlorohydrin ether, removing the unreacted epichlorohydrin from said chlorohydrin ether and subjecting said chlorohydrin ether to substantially complete dehydrochlorination.

2. Process as defined in claim 1 wherein the polyhydric phenol is bis(4-hydroxy phenyl)dimethylmethane.

3. Process as defined in claim 1 wherein the quaternary ammonium compound is tetramethyl ammonium chloride.

4. Process as defined in claim 1 wherein the quaternary ammonium compound is benzyl trimethyl ammonium chloride.

5. Process as defined in claim 1 wherein the quaternary ammonium compound is tetraethanol ammonium chloride.

6. Process as defined in claim 1 wherein the quaternary ammonium compound is tetraethanol ammonium hydroxide.

7. Process as defined in claim 1 wherein the quaternary ammonium compound is dodecyl dimethyl benzyl ammonium naphthenate.

8. Process as defined in claim 1 wherein the mixture, during the conversion of substantially all of the said phenol to its chlorohydrin ether, is, free of organic hydroxylated solvents.

9. Process for the preparation of glycidyl polyethers of polyhydric phenols which comprises reacting at a temperature below about ,60" C. a substantially anhydrous mixture containing a polyhydric phenol, epichlorohydrin in an amount suflicient to provide at least about 3 moles of epichlorohydrin per phenolic hydroxyl group, and a catalytic amount of a base-generating quaternary ammonium compound on reaction with epichlorohydrin,

until substantially all of the said phenol has been converted to its chlorohydrin ether, removing the unreacted 7g epichlorohydrin from said chlorohydrin ether and subjecting said chlorohydrin ether to substantially complete dehydrochlorination by adding thereto an excess of .the stoichiometric amount of caustic required for complete dehydrochlorination.

10. Process as defined in claim '9 wherein the reaction mixture, during the conversion of substantially all of the said phenol to its chlorohydrin ether, is free of organic hydroxylated solvents.

11. Process as defined in claim 9 wherein the amount of caustic added to dehydrochlorinate the intermediate chlorohydrin ether is 5% in excess of the stoichiometric amount.

12. Process for the preparation of glycidyl polyethers of polyhydric phenols which comprises reacting a substantially anhydrous mixture containing a polyhydric phenol, epichlorohydrin in an amount sufficient to provide at least about 3 moles of epichlorohydrin per phenolic hydroxyl group, and a catalytic amount of a base-generating quaternary ammonium compound on reaction with epichlorohydrin, until substantially all of the said phenol has been converted to its chlorohydrin ether, removing the unreacted epichlorohydrin from said chlorohydrin ether, solvating the said chlorohydrin ether with an organic solvent comprising a mixture of a watersoluble liquid selected from the group consisting of alcohols, ketones, and dioxane, and a water-insoluble liquid selected from the group consisting of hydrocarbons and isopropyl ether, subjecting said chlorohydrin ether to substantially complete dehydrochlorination by adding to said chlorohydrin ether a substantially stoichiometric amount of caustic required for complete dehydrochlorina- U011.

13. Process as defined in claim 12 wherein the ratio of water-soluble solvent to water-insoluble solvent is 1:3.

14. Process as defined in claim 12 wherein the waterinsoluble solvent is toluene.

15. Process as defined in claim 12 wherein 'the watersoluble solvent is ethanol.

16. Process for the preparation of glycidyl polyethers of polyhydric phenols which comprises reacting a mixture containing a polyhydric phenol, epichlorohydrin in an amount sufiicient to provide at least about 3 moles of epichlorohydrin per phenolic hydroxyl group, and a catalytic amount of a base-generating quaternary ammonium compound on reaction with epichlorohydrin unitl substantially all of the said phenol has been converted to its chlorohydrin ether, removing the unreacted epichlorohydrin and glycerol dichlorohydrin from said chlorohydrin ether, solvating said chlorohydrin ether with an organic solvent comprising a mixture of a watersoluble liquid and a water-insoluble liquid, adding to said solvated ether an aqueous solution of a caustic in an amount of about of the stoichiometric amount required for complete dehydrochlorination of said ether, thereby forming a two-phase mixture comprising an aque ous layer containing the chloride salt of said caustic and the catalyst residue, and an organic layer containing glycidyl polyether and chlorohydrin ether, separating the aqueous layer from the organic layer, adding to said organic layer a sufiicient amount of caustic to substantially complete the dehydrochlorination of the said chlorohydrin ether, whereby an aqueous layer and organic layer are formed, separating said aqueous layer from said organic layer and recovering the glycidyl polyether from said organic layer.

References Cited in the file of this patent UNITED STATES PATENTS 2,712,000 Zech June 28, 1955 2,744,691 Schroeder et al. Dec. 18, '1956 2,772,296 Mueller Nov. 27, 1956 2,809,942.. Cooke Oct. 15, 1957 

1. PROCESS FOR THE PREPARATION OF GLYCIDYL OF POLYETHERS OF POLYHYDRIC PHENOLS WHICH COMPRISES REACTING A SUBSTANTIALLY ANHYDROUS MIXTURE CONTAINING A POLYHYDRIC PHENOL, EPICHLOROHYDRIN IN AN AMOUNT SUFFICIENT TO PROVIDE AT LEAST ABOUT 3 MOLES OF EPICHLOROHYDRIN PER PHENOLIC HYDROXYL GROUP, AND A CATALYTIC AMOUNT OF A BASE-GENERATING QUATERNARY AMMONIUM COMPOUND ON REACTION WITH EPICHLOROHYDRIN, UNTIL SUBSTANTIALLY ALL OF THE SAID PHENOL HAS BEEN CONVERTED TO ITS CHLOROHYDRIN ETHER, REMOVING THE UNREACTED EPICHLOROHYDRIN FROM SAID CHLOROHYDRIN ETHER AND SUBJECTING SAID CHLOROHYDRIN ETHER TO SUBSTANTIALLY COMPLETE DEHYDROCHLORINATION. 